CN113485072B - Photoresist composition and application thereof - Google Patents
Photoresist composition and application thereof Download PDFInfo
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- CN113485072B CN113485072B CN202110691354.5A CN202110691354A CN113485072B CN 113485072 B CN113485072 B CN 113485072B CN 202110691354 A CN202110691354 A CN 202110691354A CN 113485072 B CN113485072 B CN 113485072B
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 141
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000000654 additive Substances 0.000 claims abstract description 29
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 239000004014 plasticizer Substances 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 15
- 239000005011 phenolic resin Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 25
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 24
- 229920003986 novolac Polymers 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- -1 ester compounds Chemical class 0.000 claims description 15
- 239000003504 photosensitizing agent Substances 0.000 claims description 10
- 238000011161 development Methods 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- 238000012643 polycondensation polymerization Methods 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 4
- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- LLBBBYLDTDJMNU-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(O)C=C1O LLBBBYLDTDJMNU-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 230000009969 flowable effect Effects 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000010992 reflux Methods 0.000 abstract description 5
- 230000002411 adverse Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 2
- APVNRHLATFVPPS-UHFFFAOYSA-N (2-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1O APVNRHLATFVPPS-UHFFFAOYSA-N 0.000 description 1
- SRUQARLMFOLRDN-UHFFFAOYSA-N 1-(2,4,5-Trihydroxyphenyl)-1-butanone Chemical compound CCCC(=O)C1=CC(O)=C(O)C=C1O SRUQARLMFOLRDN-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- 102100039386 Ketimine reductase mu-crystallin Human genes 0.000 description 1
- 101000772180 Lithobates catesbeianus Transthyretin Proteins 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
The application provides a photoresist composition and application thereof, wherein the photoresist composition comprises the following components in parts by weight: 10-50 parts of phenolic resin, 1-10 parts of sensitizer, 0.1-5 parts of plasticizer, 0.1-5 parts of additive and 40-100 parts of organic solvent, wherein the additive comprises at least one of compounds shown in a structural formula (I). The photoresist disclosed by the application is used as a G line photoresist or an I line photoresist, has a lower reflux temperature, can avoid adverse effects on devices caused by high temperature, can be quickly refluxed at a lower temperature to form a micromirror array with good morphology, and can be used in a production process with severe temperature requirements. And the micro mirror array with good appearance can be formed by reflow of the pattern with smaller size or larger aspect ratio.
Description
Technical Field
The application relates to the technical field of micro-electromechanical systems or organic light-emitting diodes, in particular to a photoresist composition and application thereof.
Background
In recent years, the use of optical devices has increased dramatically, and it is common to implant very complex multifunctional instruments such as smartphones or cameras. At the heart of this type of optics is an array of micromirrors that are used for the collection or emission of light. Currently, the most common method of industrially manufacturing micromirror arrays is thermal reflow of photoresist. The photoresist serves as a pattern transfer, i.e., transferring a pattern from a reticle to a corresponding substrate. One of the most common methods is: photoresist is coated on a substrate, exposure and development are carried out to obtain a pattern, which is usually a pattern of lines, columns or cylinders arranged regularly, and then the pattern is heated and reflowed to flow into a semicircle.
Typically, the glass transition temperature (Tg) of the resin in the photoresist is 100-120 ℃, but the unexposed photosensitizer in the photoresist can be decomposed at high temperature to serve as a crosslinking agent to initiate resin crosslinking, the Tg of the crosslinked resin is 140-150 ℃, and in order to obtain better micro-mirror morphology, the reflow temperature is at least 50 ℃ higher than the Tg, namely above 200 ℃. However, due to the limitation of the production process with severe temperature requirements, too high a temperature cannot be used, and therefore, development of a photoresist with a lower reflow temperature is needed.
Disclosure of Invention
In view of the foregoing problems of the prior art, an object of the present application is to provide a photoresist composition and use thereof to achieve a reduction in reflow temperature.
The first aspect of the present application provides a photoresist composition comprising, in parts by weight: 10-50 parts of linear phenolic resin, 1-10 parts of photosensitizer, 0.1-5 parts of plasticizer, 0.1-5 parts of additive and 40-100 parts of organic solvent;
the additive comprises at least one of compounds shown in a structural formula (I):
wherein R is 1 -R 5 Each independently selected from hydrogen, halogen, hydroxy, ether, ester, phenyl, C 1 -C 10 Alkyl, C of (2) 3 -C 10 A cycloalkyl group, a sulfonic acid group unsubstituted or substituted with Ra, an amino group unsubstituted or substituted with Ra;
the Ra are each independently selected from C 6 -C 10 Cycloalkyl or phenyl.
A second aspect of the present application provides the use of the photoresist composition of the present application as a G-line photoresist or I-line photoresist.
The photoresist composition provided by the application comprises the following components in parts by weight: 10-50 parts of phenolic resin, 1-10 parts of sensitizer, 0.1-5 parts of plasticizer, 0.1-5 parts of additive and 40-100 parts of organic solvent, wherein the additive comprises at least one of compounds shown in a structural formula (I). The addition of the additive makes the photoresist composition of the present application more flowable at low temperatures to obtain better micromirror morphology. The additive can not be bleached and absorbed in the G line and the I line, and after light development, the shape of the micro mirror array is more trapezoidal, so that the micro mirror array is more convenient for flow forming. The photoresist disclosed by the application is used as a G line photoresist or an I line photoresist, can be quickly reflowed at a lower temperature to form a micromirror array with good morphology, and can be used in a production process with severe temperature requirements. And the micro mirror array with good appearance can be formed by reflow of the pattern with smaller size or larger aspect ratio.
Of course, it is not necessary for any one product or method of practicing the application to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it is apparent that the drawings in the description below are only one embodiment of the present application, and other embodiments may be obtained according to these drawings by those skilled in the art.
FIGS. 1a, 1b and 1c are schematic diagrams of the fabrication of a micromirror array according to one embodiment of the application;
FIGS. 2a and 2b show the photoresist profile before and after reflow in example 1 of the present application;
FIGS. 3a and 3b show the photoresist profile before and after reflow in example 2 of the present application;
FIGS. 4a and 4b show the photoresist patterns before and after reflow in example 3 of the present application;
FIGS. 5a and 5b show the photoresist profile before and after reflow in example 4 of the present application;
FIGS. 6a and 6b show the photoresist profile before and after reflow in example 5 of the present application;
FIGS. 7a and 7b are graphs of photoresist patterns before and after reflow in example 6 of the present application;
FIGS. 8a and 8b are photoresist profiles before and after reflow in example 7 of the present application;
FIGS. 9a and 9b are photoresist profiles before and after reflow in example 8 of the present application;
FIGS. 10a and 10b show the photoresist profile before and after reflow in example 9 of the present application;
fig. 11a and 11b show the photoresist profiles before and after reflow in comparative example 1 according to the present application.
Reference numerals: 10. the device comprises a substrate, 20, a photoresist pattern of a cylindrical structure, 30, a micromirror array, 31, a photoresist pattern of a hemispherical structure, 40, a photoresist layer and 50, and a mask plate.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments obtained by those skilled in the art based on the embodiments of the present application are within the scope of the present application.
The first aspect of the present application provides a photoresist composition comprising, in parts by weight: 10-50 parts of linear phenolic resin, 1-10 parts of photosensitizer, 0.1-5 parts of plasticizer, 0.1-5 parts of additive and 40-100 parts of organic solvent; preferably, 15-40 parts of linear phenolic resin, 2-8 parts of sensitizer, 0.1-2 parts of plasticizer, 0.1-2 parts of additive and 50-80 parts of organic solvent; the additive comprises at least one of compounds shown in a structural formula (I):
wherein R is 1 -R 5 Each independently selected from hydrogen, halogen, hydroxy, ether, ester, phenyl, C 1 -C 10 Alkyl, C of (2) 3 -C 10 A cycloalkyl group, a sulfonic acid group unsubstituted or substituted with Ra, an amino group unsubstituted or substituted with Ra; the Ra is each independently selected from C 6 -C 10 Cycloalkyl or phenyl.
Preferably, the additive may comprise at least one of the following compounds D1-D4:
it will be appreciated by those skilled in the art that in the present application, the above "parts" are not limited to specific mass units, and those skilled in the art can choose according to actual situations, and only need to be added in proportion. For example: g. kg or t, etc.
The additive provided by the application flows more easily at low temperature, so that the photoresist composition can be quickly reflowed to form a micromirror array with good morphology at a low temperature of less than or equal to 110 ℃. In addition, the additive can not be bleached and absorbed in the G line and the I line, and after light development, the shape of the micro mirror array is more trapezoidal, so that the micro mirror array is more convenient for flow forming.
The photoresist composition has lower reflux temperature, can avoid the crosslinking temperature of resin, can quickly reflux at a low temperature of less than or equal to 110 ℃ to form a hemispherical micromirror array with good appearance, and can be used in a production process with strict temperature requirements. And the method still meets the reflow process for the patterns with smaller size or larger height-width ratio, does not have the phenomenon of protruding top, and can reflow to form the micro-mirror array with good appearance.
In one embodiment of the present application, the components of the photoresist composition may further include a leveling agent, etc. In the present application, the kind of leveling agent is not particularly limited as long as the object of the present application can be achieved. For example, the leveling agent may be selected from at least one of an ionic surfactant and a nonionic surfactant. Preferably a nonionic surfactant. Specifically, it may include a FC-4430 surfactant (manufacturer: 3M company in the United states), a FC-4432 surfactant (manufacturer: 3M company in the United states), a fluoro-diol, POLYFOX PF-636 (manufacturer: european Union (Shanghai)) a POLYFOX PF-6320 (manufacturer: european Union (Shanghai)) a POLYFOX PF-656 (manufacturer: european Union (Shanghai)) a POLYFOX PF-6520 (manufacturer: european Union (Shanghai)) and the like. The amount of the leveling agent used in the present application is not particularly limited as long as the object of the present application can be achieved. The use of the leveling agent can reduce the surface tension between the phenolic novolac resin, the photosensitizer, the plasticizer and the organic solvent in the photoresist composition, so that the phenolic novolac resin, the photosensitizer and the plasticizer are uniformly dispersed in the organic solvent. Further, the linear resin, the photosensitizer and the plasticizer in the photoresist layer obtained by coating the photoresist composition are uniformly distributed, so that the photoresist layer can be prevented from being spotted or linear marks.
In one embodiment of the present application, the phenolic novolac resin includes at least one of polycondensates formed by condensation polymerization of cresol compounds and aldehydes. In the present application, the p-cresol compound is not particularly limited as long as the object of the present application can be achieved. For example, the cresol compound may include at least one of m-cresol, p-cresol, o-cresol, xylenol, and tricresyl. In the present application, the aldehyde compound is not particularly limited as long as the object of the present application can be achieved. For example, the aldehyde compound may include at least one of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and salicylaldehyde.
Preferably, the phenolic novolac resin comprises a polycondensate formed by condensation polymerization of m-cresol and p-cresol with formaldehyde, wherein the molar ratio of the m-cresol to the p-cresol is 1:1-1:4, preferably 1:1-1:2.5.
The phenolic novolak resin according to any of the preceding embodiments, is capable of improving the chemical resistance and adhesion of the photoresist composition. The novolac resin of the foregoing preferred embodiment can more remarkably improve the chemical resistance and adhesion of the photoresist composition.
In one embodiment of the application, the weight average molecular weight of the phenolic novolac resin is in the range of 2000 to 15000, preferably 2000 to 8000, more preferably 3000 to 5000. The weight average molecular weight of the phenolic novolac resin is too small (for example, less than 2000), the heat resistance of the phenolic novolac resin is reduced, and the phenomenon of softening and flowing of the photoresist is easily caused; the excess weight average molecular weight of the phenolic novolac resin (e.g. greater than 15000) and the lower sensitivity of the phenolic novolac resin will result in an increase in the energy required to expose the photoresist layer. By controlling the weight average molecular weight of the novolac resin within the above range, the photoresist has high heat resistant temperature and good photosensitivity.
In one embodiment of the present application, the sensitizer comprises a compound formed by reacting diazonaphthoquinone with a polycyclic compound having a plurality of phenolic hydroxyl groups; wherein the molar ratio of the diazonaphthoquinone to the polycyclic compound with a plurality of phenolic hydroxyl groups is 1:1-1:4, preferably 1:2-1:3.
In the present application, the kind of the diazonaphthoquinone is not particularly limited as long as the object of the present application can be achieved. For example, the diazonaphthoquinone may be selected from 2-diazonaphthoquinone-1-naphthoquinone-4-sulfonyl chloride or 2-diazonaphthoquinone-1-naphthoquinone-5-sulfonyl chloride. In the present application, the type of the polycyclic compound having a plurality of phenolic hydroxyl groups is not particularly limited as long as the object of the present application can be achieved. For example, the polycyclic compound having a plurality of phenolic hydroxyl groups may be selected from the group consisting of 2,3, 4-trihydroxybenzophenone, 2',4' -tetrahydroxybenzophenone, 2', any one of 3, 4-tetrahydroxybenzophenone, 2,3, 4' -Tetrahydroxybenzophenone (THBP), 1-tris (4-hydroxyphenyl) ethane or 1, 1-tris (4-hydroxyphenyl) methane, preferably 2,2', 4' -tetrahydroxybenzophenone or 2,2',3, 4-tetrahydroxybenzophenone.
For example, the sensitizer may include at least one of the following compounds B1 and B2. Wherein, the compound B1 is formed by the reaction of 2,3,4 '-tetrahydroxybenzophenone and 2-diazonium-1-naphthoquinone-5-sulfonyl chloride (DNQ) according to the mol ratio of 1:2, and the compound B2 is formed by the reaction of 2,3, 4' -tetrahydroxybenzophenone and 2-diazonium-1-naphthoquinone-5-sulfonyl chloride according to the mol ratio of 1:3.
The photosensitive agent of the application contains diazonaphthoquinone and polycyclic compound with a plurality of phenolic hydroxyl groups, so that the photoresist composition has photosensitive property, can generate chemical reaction after exposure, and can be dissolved in a developing solution.
In one embodiment of the present application, the plasticizer is selected from at least one of epoxy compounds, ester compounds, ether compounds, polyhydroxy compounds, and polymers thereof. Preferably, the plasticizer is at least one selected from the group consisting of 4,4- (1-isopropylidene) bis (2, 6-bisphenol) (C1), 2',4' -tetrahydroxybenzophenone, 2,3,4 '-tetrahydroxybenzophenone, 2',4 '-dihydroxypropiophenone, 2,4' -dihydroxydiphenylmethane, dibutyl phthalate, diethyl phthalate, di (2-ethylhexyl) phthalate, methyl vinyl ether and polymethyl vinyl ether. The use of plasticizers of the above type can increase the photospeed, resulting in a reduction in the energy required to expose the photoresist composition to light, allowing the photoresist composition to flow at lower temperatures, and thus can also improve the lithographic efficiency.
In one embodiment of the present application, the organic solvent is selected from at least one of Propylene Glycol Methyl Ether Acetate (PGMEA), propylene Glycol Methyl Ether (PGME), diheptanone, methyl isobutyl ketone, ethyl lactate, anisole, cyclopentanone, xylene, ethyl acetate, and butyl acetate. Preferably at least one selected from PGMEA, ethyl lactate and di-heptanone. The organic solvent has good dissolution property and coating property, and the linear phenolic resin, the photosensitive agent, the plasticizing agent and the additive in the photoresist composition can be more uniformly dissolved in the organic solvent by selecting the organic solvent, so that the linear phenolic resin, the photosensitive agent, the plasticizing agent and the additive in the photoresist layer formed by the photoresist composition are more uniformly distributed.
In the present application, the method of preparing the photoresist composition is not particularly limited as long as the object of the present application can be achieved. For example, the method of preparing the photoresist composition of the present application may include the steps of: dissolving the linear phenolic resin, the photosensitizer, the plasticizer and the additive in an organic solvent, and uniformly mixing to obtain a photoresist composition; wherein, the weight portions of the phenolic resin are 10 to 50 portions, 1 to 10 portions of the photosensitizer, 0.1 to 5 portions of the plasticizer, 0.1 to 5 portions of the additive and 40 to 100 portions of the organic solvent.
It should be noted that, since Ultraviolet (UV) is included in natural light, in order to prevent chemical reaction from occurring due to UV during the preparation of the photoresist composition, the chemical stability of the photoresist composition is affected, and in one embodiment of the present application, the photoresist composition is prepared in an environment without UV. For example, the linear phenolic resin, the photosensitizer, the plasticizer and the additive are dissolved in an organic solvent under a yellow light environment and uniformly mixed, so that the photoresist composition is obtained.
In the present application, the order of mixing the above-mentioned novolac resin, sensitizer, plasticizer, additive and organic solvent, mixing time, and mixing temperature are not particularly limited as long as the object of the present application can be achieved.
The second aspect of the present application provides the use of the photoresist composition of the present application as a G-line photoresist or an I-line photoresist. Wherein, the photoresist composition of the application is used as G line photoresist, and the exposure light source has a wavelength of 436nm. The photoresist composition of the present application was used as an I-line photoresist, and the exposure light source was 365nm in wavelength.
Photoresist refers to an etching-resistant thin film material whose solubility is changed by irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, or the like. Typically used as a material for a corrosion resistant coating during a lithographic process. Photoresists can be classified into positive photoresists and negative photoresists according to the chemical reaction mechanism and development principle of the photoresist. The exposed areas of the positive photoresist undergo a photolytic reaction, degrading the photoresist into a substance that is soluble in the developer, thereby enabling the non-exposed areas of the photoresist to form a photoresist pattern that is the same or substantially the same as the mask pattern. The exposed areas of the negative photoresist undergo a cross-linking reaction and are insoluble in the developer, and the unexposed areas are soluble in the developer, thereby enabling the unexposed areas of the photoresist to form a photoresist pattern that is complementary or substantially complementary to the mask pattern.
The photoresist composition provided by the application is used as a G line photoresist or an I line photoresist, and is a positive photoresist, namely, the photoresist composition is insoluble in a developing solution before exposure, and after exposure, the chemical property of the part subjected to illumination is converted and can be dissolved in the developing solution so as to be removed.
The photoresist of the present application can be used as a base material for manufacturing a micromirror array. In the present application, the method of manufacturing the micromirror array is not particularly limited as long as the object of the present application can be achieved. For example, the present application may employ a method of manufacturing a micromirror array comprising the steps of:
(1) Forming a photoresist layer having a thickness of 1-2 μm on a surface of a substrate, the photoresist layer comprising the photoresist composition of the present application;
(2) Exposing the photoresist layer by using a mask plate;
(3) Developing the exposed photoresist layer to obtain a photoresist pattern;
(4) And baking the photoresist pattern to reflow the photoresist pattern, thereby obtaining the micro-mirror array.
In the present application, the term "micromirror array" refers to an array of lenses with clear apertures and relief depths on the order of micrometers.
The method of forming the photoresist layer, exposing and developing is not particularly limited in the present application, as long as the object of the present application can be achieved. For example, the photoresist layer may be formed by spraying, flowing, dipping, rolling, or spin coating, etc. The method of exposure may include contact exposure, proximity exposure, projection exposure, or the like. The developing method can comprise immersion developing, continuous spray developing or puddle developing of the whole box silicon wafer. The developing solution to be used in the development is not particularly limited as long as the object of the present application can be achieved. For example, the developer may include tetramethylammonium hydroxide, and the like.
In the step (4), the reflow temperature of the photoresist pattern is less than or equal to 110 ℃, so that the photoresist pattern can be quickly reflowed at a low temperature to form a semicircular micromirror array with good morphology. The time of the reflow is not particularly limited as long as the object of the present application can be achieved.
In one embodiment of the present application, as shown in FIG. 1a, a photoresist layer 40 having a thickness of 1-2 μm is coated on a substrate 10, ultraviolet exposure is performed under a circular array of mask plates 50, and the exposed photoresist layer 40 is developed; as shown in fig. 1b, a photoresist pattern 20 of a cylindrical structure is obtained after development; as shown in fig. 1c, the photoresist pattern 20 of the cylindrical structure is heated to a molten state, and reflowed, and its surface tension converts the photoresist pattern 20 of the cylindrical structure into the photoresist pattern 31 of the hemispherical structure, thereby obtaining the micromirror array 30.
The photoresist composition is used as G line photoresist or I line photoresist to manufacture a micro-mirror array, can obtain a hemispherical micro-mirror array with good appearance at a low reflux temperature of less than or equal to 110 ℃, and can reflow a pattern with small size or large aspect ratio to form a micro-mirror array with good appearance, and the resolution is high.
The following examples and comparative examples are given to more specifically explain embodiments of the present application. The experiments and evaluations of each example and comparative example were performed in the following manner. Unless otherwise specified, "parts" and "%" are mass references.
Test method and equipment:
the resolution test method comprises the following steps:
(1) Spin coating is carried out on a 6-inch silicon wafer by using a gumming machine (manufacturer: tokyo electronic Co., ltd., model: mark V), the rotation speed of the spin coating is adjusted according to the thickness of the photoresist layer, after the spin coating is finished, the first baking is carried out, the temperature is 90 ℃ and the time is 60 seconds, and then the film thickness measurement is carried out by cooling, so that the photoresist layer with the thickness of 2 mu m is formed;
(2) Then, putting the mask plate into an I line exposure machine (manufacturer: nikon Co., ltd., model: nikon I9, numerical Aperture (NA) =0.57) for exposure, wherein the mask plate is provided with a line width of 2-0.25 mu m, the ratio of the line width to the grating spacing is 1:1-1:5, the exposure time is set to be 20-2000ms for exposure, and the exposure quantity is 10-1000mJ;
(3) Then, development was carried out with an aqueous solution of 2.38wt% tetramethylammonium hydroxide at 23℃for 60 seconds;
(4) Finally, the resolution was evaluated using a photo-resist image obtained by a scanning electron microscope (CD-SEM) for feature size measurement (manufacturer: hitachi, model 8840).
Reflux performance test:
the wafer observed by the CD-SEM is placed on a hot plate again for baking, the reflow temperature is 105-110 ℃, the reflow time is 90-180s, and the appearance of the reflowed photoresist is observed by X-SEM section (manufacturer: hitachi, model 4800).
And (3) testing the photosensitive speed:
using the exposure quantity, namely exposure energy, in the step (2) of the resolution test method: when the line width measured on the photoresist picture is consistent with the actual value on the mask, the optimal exposure of the line width is obtained, and the value of the photosensitive speed of the formula is obtained as the result of the photosensitive speed.
Example 1
< preparation of Photoresist composition >
20 parts of a novolac resin A1, 3 parts of a sensitizer B2, 1 part of a plasticizer C1, 0.3 part of an additive D1 and 0.01 part of a leveling agent fluoro-diol were dissolved in 57 parts of PGMEA to prepare a solution with a solid content of 30%, and the solution was filtered through a filter membrane with a pore size of 0.2. Mu.m, to obtain a photoresist composition. Wherein, the linear phenolic resin A1 is prepared by condensation polymerization reaction of m-cresol and p-cresol with formaldehyde, the molar ratio of the m-cresol to the p-cresol is 1:1.5, and the weight average molecular weight of A1 is 3750.
< preparation of micromirror array >
Forming a photoresist layer with the thickness of 2 mu m on the surface of the substrate, wherein the photoresist layer adopts the photoresist composition;
exposing the photoresist layer by using a mask plate;
developing the exposed photoresist layer to obtain a photoresist pattern with the height of 0.7 μm, as shown in fig. 2 a;
the photoresist pattern was baked on a hot plate to be reflowed at 110 c for 60s, resulting in a micromirror array having a height of 0.7 μm as shown in fig. 2 b.
Example 2
The procedure of example 1 was repeated except that D2 was used as the additive in < preparation of resist composition >.
Example 3
The procedure of example 1 was repeated except that 1 part by mass of the photosensitive agent B2 and 1 part by mass of the additive D3 were used in the < preparation of the photoresist composition >.
Example 4
The procedure of example 1 was repeated except that D4 was used as the additive in < preparation of resist composition >.
Example 5
The procedure of example 1 was repeated except that in < preparation of resist composition > A2 was used as the novolac resin. Wherein, the linear phenolic resin A2 is formed by condensation polymerization reaction of m-cresol and p-cresol with formaldehyde, the molar ratio of the m-cresol to the p-cresol is 1:1, and the weight average molecular weight of A2 is 6000.
Example 6
The procedure of example 1 was repeated except that in < preparation of resist composition > A3 was used as the novolac resin. Wherein, the linear phenolic resin A3 is prepared by condensation polymerization of m-cresol and p-cresol with formaldehyde, the molar ratio of the m-cresol to the p-cresol is 1:1, and the weight average molecular weight of A3 is 7000.
Example 7
The procedure of example 1 was repeated except that in < preparation of resist composition > B1 was used as the sensitizer.
Example 8
The procedure of example 1 was repeated except that in < preparation of a photoresist composition >, a mixture of b1:b2=1:1 was used as the sensitizer.
Example 9
The procedure of example 1 was repeated except that the reflow temperature was 105℃in the < preparation of micromirror array >.
Comparative example 1
The procedure of example 1 was repeated except that no additive was used in the preparation of the photoresist composition.
The preparation parameters and test results for examples 1-8 and comparative example 1 are shown in Table 1:
TABLE 1
Note that: the "/" in Table 1 indicates that there are no corresponding preparation parameters.
As can be seen from table 1 and fig. 2 to 11, the resolution, the photosensitive speed of the photoresist compositions in examples 1 to 9 are generally significantly better than those of the photoresist composition of comparative example 1. The micromirror array prepared by the photoresist composition of examples 1-9 is a semicircular or near semicircular micromirror array with good morphology; and the micro mirror array prepared by the photoresist composition of comparative example 1 has obvious protrusions on the top. Therefore, the photoresist composition provided by the application has low reflow temperature, high resolution and high photosensitive speed, and can be quickly reflowed to form a good hemispherical micro-mirror array at the low reflow temperature of less than or equal to 110 ℃.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application are included in the protection scope of the present application.
Claims (8)
1. A photoresist composition comprises the following components in parts by weight: 10-50 parts of linear phenolic resin, 1-10 parts of photosensitizer, 0.1-5 parts of plasticizer, 0.1-5 parts of additive and 40-100 parts of organic solvent;
the additive comprises at least one of the following compounds D1-D4:
the addition of the additive makes the photoresist composition more flowable at low temperature to obtain better micromirror morphology; the additive can not be bleached and absorbed in the G line and the I line, and after light development, the shape of the micro mirror array is more trapezoidal, so that the micro mirror array is more convenient for flow forming;
the linear phenolic resin comprises polycondensate formed by condensation polymerization of m-cresol and p-cresol with formaldehyde, wherein the molar ratio of the m-cresol to the p-cresol is 1:1-1:4;
the weight average molecular weight of the phenolic novolac resin is 2000-15000.
2. The photoresist composition of claim 1, wherein the molar ratio of m-cresol to p-cresol is 1:1-1:2.5.
3. The photoresist composition of claim 1, wherein the novolac resin has a weight average molecular weight of 2000-8000.
4. The photoresist composition of claim 1, wherein the novolac resin has a weight average molecular weight of 3000-5000.
5. The photoresist composition of claim 1, wherein the plasticizer is selected from at least one of epoxy compounds, ester compounds, ether compounds, polyhydroxy compounds, and polymers thereof.
6. The photoresist composition of claim 1, wherein the plasticizer is selected from at least one of 4,4- (1-isopropylidene) bis (2, 6-bisphenol), 2',4' -tetrahydroxybenzophenone, 2,3,4 '-tetrahydroxybenzophenone, 2',4 '-dihydroxypropiophenone, 2,4' -dihydroxydiphenylmethane, dibutyl phthalate, diethyl phthalate, di (2-ethylhexyl) phthalate, methyl vinyl ether, and polymethyl vinyl ether.
7. The photoresist composition of claim 1, wherein the organic solvent is selected from at least one of propylene glycol methyl ether acetate, propylene glycol methyl ether, diheptanone, methyl isobutyl ketone, ethyl lactate, anisole, cyclopentanone, xylene, ethyl acetate, and butyl acetate.
8. Use of the photoresist composition of any one of claims 1-7 as a G-line photoresist or an I-line photoresist.
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| CN1646991A (en) * | 2002-04-18 | 2005-07-27 | 日产化学工业株式会社 | Positively photosensitive resin composition and method of pattern formation |
| CN1930522A (en) * | 2004-03-12 | 2007-03-14 | 东丽株式会社 | Positive light-sensitive resin composition, relief pattern using the same, and solid imaging element |
| CN101727002A (en) * | 2008-10-28 | 2010-06-09 | Jsr株式会社 | Radiation-sensitive resin composition, interlayer insulating film and microlens, and method for forming the same |
| CN103217728A (en) * | 2013-03-21 | 2013-07-24 | 广州中国科学院先进技术研究所 | Micro-lens array with filtering function and preparation method thereof |
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|---|---|---|---|---|
| CN1646991A (en) * | 2002-04-18 | 2005-07-27 | 日产化学工业株式会社 | Positively photosensitive resin composition and method of pattern formation |
| CN1930522A (en) * | 2004-03-12 | 2007-03-14 | 东丽株式会社 | Positive light-sensitive resin composition, relief pattern using the same, and solid imaging element |
| CN101727002A (en) * | 2008-10-28 | 2010-06-09 | Jsr株式会社 | Radiation-sensitive resin composition, interlayer insulating film and microlens, and method for forming the same |
| CN103217728A (en) * | 2013-03-21 | 2013-07-24 | 广州中国科学院先进技术研究所 | Micro-lens array with filtering function and preparation method thereof |
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